Water- and oil repellency agents

ABSTRACT

FLUOROALKYL-ALKOXYALKYL ACRYLATES AND METHACRYLATES COMPRISING THE REACTION PRODUCT OF A PERFLUOROALKOXYALKYL ALKANOL AND AN ACRYLIC OR METHACRYLIC ACID REAGENT. THE RESULTING MONOMERS MAY, THEREAFTER BE HOMO- OR COPOLYMERIZED WITH A WIDE VARIETY OF CONVENTIONAL ETHYLENICALLY UNSATURATED, I.E. VINYL, MONOMERS, SAID POLYMERIC MATERIALS IMPARTING BOTH WATER AND OIL REPELLENCY TO A WIDE VARIETY OF SUBSTRATES.

United States Patent Oifiee 3,660,366 Patented May 2, 1972 3,660,360 WATER- AND OIL REPELLEN CY AGENTS Dilip K. Ray-Chaudhuri and Carmine P. Iovine, Somerset, N.J., assignors to National Starch and Chemical Corporation, New York, N.Y. No Drawing. Filed June 24, 1970, Ser. No. 49,537 Int. Cl. C08t /38, 29/38, 37/00 U.S. Cl. 260-785 E 12 Claims ABSTRACT OF THE DISCLOSURE SUMMARY OF THE INVENTION It is the object of this invention to provide a novel class of fluoroalkyl-alkoxyalkyl acrylate and methacrylate esters, said esters being capable of undergoing vinyl type polymerizations either alone or in the presence of other vinyl type monomers. A further object of this invention is to utilize these compositions to treat substrates exhibiting either fibrous, porous or continuous surfaces and thereby provide said substrates with a high degree of Water, oil and soil repellency. Various other objects and advantages of this invention will become apparent to the practitioner from the following description thereof.

Thus, the novel monomeric compositions of this invention comprise the fluoroal-kyl-alkoxyalkyl acrylate and methacrylate esters corresponding to the following formula:

wherein Z is a radical containing from 3 to carbon atoms inclusive and is selected from the group consisting of straight and branched chain perfiuoro alkyl radicals; perfluoro cyclo aliphatic radicals; and, straight and branched chain perfluoro alkyl and perfluoro cyclo aliphatic radicals wherein the perfluoro group is substituted with at least one atom selected from the group consisting of hydrogen, chlorine, bromine and iodine atoms;

X is a radical selected from the group consisting of straight and branched chain alkenylene and alkylene radicals containing from 1 to 20 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl radicals containing from .1 to 20 carbon atoms, aromatic radicals, and cycloaliphatic radicals;

R is selected from the group consisting of hydrogen and methyl radicals; and, V

n is an integer having a value of from 1 to 10 inclusive.

As previously noted, materials which have been treated with the novel fiuoro compositions of this invention exhibit water, oil and soil repellency. Among the primary avantages derived from the use of these additives are included::

(1) the ability to use a single additive in order to acquire a large number of desired properties;

(2) the applicability of these additives to a wide variety of substrates, e.g. textiles, paper, etc.;

(3) the prolonged retention of the properties imparted by these novel additives despite repeated wet laundering and/or dry cleaning;

'(4) the ease with which substrates may be treated with these additives; and,

(5) the soft hand and drape which is also imparted to the thus treated fabrics, etc.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In brief, the procedure for preparing the fluoroalkylalkoxyalkyl acrylate and methacrylate esters of this invention comprises reacting (.1) a perfluoroalkoxyalkyl alkanol with (2) an acrylic or methacrylic acid reagent.

The perfluoroal koxyallryl alkanol applicable for use in the process of this invention correspond to the formula:

wherein Z, X, R and n are as previously identified.

Thus, among the applicable perfluoroalkoxyalkyl alkanols are included:

ethylene glycol, mono-(a,u-dihydroperfluorooctyl) ether,

i.e. CI1F15CH20CH2CH2OH diethylene glycol, mono-(a dihydroperfluorooctyl) ether, i.e. C F CH 0 (CH CH O) H;

ethylene glycol, mono-(1,1,7-trihydroperfiuoro heptyl) ether, i.e. H(OF OF CH OCH CH OH;

ethylene glycol, mono-(a,a-dihydroperfluorobutyl) ether,

diethylene glycol, mono-(a,a-dihydroperfluorobutyl) ether, i.e.

triethylene glycol, mono-(u,a-dihydroperfluorobutyl) ether, i.e. C3F7CH2O(CH2CH2O)3H;

l-methyl-ethylene glycol, mono-(u,a-dihydroperfluorooctyl) ether, i.e.

ethylene glycol, mouo-( 1 l-perfluoroheptyl] undecyl) ether, i.e. C7F15(CH2)110CH2CH2OH;

1-pheny1-ethylene glycol, mono-(a,a-dihydroperfiuorooctyl) ether, i.e.

l-ethyl-ethylene glycol, mono-(u,u-dihydroperfluorooctyl) ether, i.e.

decaethylene glycol, mono-[(S-perfluorobutyl) -n-pentyl] ether, i.e. C F (CH O(CH -CH O) H; diethylene glycol, mono-[( 12-perfiuorododecyl)-n-dodeCyHether, i.e. C12F25(CH2)1ZO(CH2 CH20)2H; octaethylene glycol, ID0110-(0:,oc-dihYdlOP6I'flllOI00CtY1) ether, i.e. C7F15CH2O 3H; propylene glycol, mono-[(l0-perfiuoropentyl)-10- undecene] ether, i.e.

C5Fu-CH=CH-(CH2)80GH -CHOH a A typical procedure for preparing the perfiuoroalkoxyalkyl alkanols comprises the reaction of a prefluoro alcohol with an alkylene oxide in the presence of an acidic or basic catalyst in a pressure vessel at a temperature of 60-120 C. for a period of about 1-24 hours. Among the applicable alkylene oxides are included: ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, 1,2-dodecene oxide and 1,2-octadecene oxide.

This reaction procedure, which is preferred for purposes of this invention, proceeds according to the following reaction mechanism:

OH- ZXH+n(CH2CHR) v Z-XO-(CHzGH--O)nH The perfluoroalkoxyalkyl alkanols can also be prepared by means of a base induced condensation reaction of the perfluoro alcohol with an omega-halo alcohol conducted either at atmospheric or super-atmospheric pressures. The reaction mechanism of this procedure is as follows:

In either instance, the usually water insoluble perfluoroalkyl ether alcohols are isolated by means of conventional extraction and distillation techniques.

The procedures which may be used for preparing the acrylate and methacrylate esters of the perfluoroalkoxyalkyl alkanol intermediates are well known to those skilled in the art. Included among such procedures are:

(1) Direct esterification wherein glacial acrylic or methacrylic acid is reacted with the alkanol intermediate, the latter esterification being effected by refluxing the reagents in the presence of an acidic catalyst, such as benzene sulfonic acid, and removing the Water formed during the course of the reaction by means of an azeotropic distillation technique;

(2) The reaction, at temperatures of from about C. to 75 C., of perfluoroalkyl ether alkanol intermediate with acrylyl or methacrylyl chloride and the simultaneous removal of the hydrogen chloride produced during the course of the reaction; and

(3) An alcoholysis technique whereby a low molecular weight acrylate or methacrylate ester such, for example, as methyl acrylate ethyl acrylate and methyl methacrylate is reacted with the perfluoroalkyl ether alkanol intermediate in either an acidic or alkaline medium at temperatures of from about 50 C. to 150 C. Regardless of the procedure utilized, the resulting acrylate and methacrylate esters may be purified by conventional means thereby resulting in products which are usually low melting solids or viscous liquids, which are highly soluble in chlorinated solvents, alcohols and acetone and which have some utility as water and oil repellency agents. In view of the variety of methods which may be used to prepare the acrylate and methacrylate esters, the term acrylic and methacrylic acid reagent, for purposes of this invention, is meant to include acrylic acid, methacrylic acid and any derivatives thereof which may be utilized to convert the alkanol intermediate to its acrylate or methacrylate equivalent.

With respect to proportions, the determination of the precise concentration of the primary reactants in relation to one another, as based on the stoichiometric equivalencies of the various reactions, is left to the discretion of the practitioner. However, typical proportions for the preparation of the intermediates and the subsequent acrylates and methacrylates include the reaction of one mole of the perfluoroalcohol with approximately 1-10 mole of the alkylene oxide and, thereafter, the reaction of the intermediate product with approximately one mole of the acrylic or methacrylic acid reagent.

In utilizing the fiuoroalkyl-alkoxyalkyl acrylates and methacrylates in the preparation of homoand copolymers, there may be employed one of the usual vinyl polymerization methods which are well known to those skilled in the art and which is particularly suited for the homoand copolymer whose preparation is desired. Thus, such polymers may be prepared by means of free radical initiated processes utilizing bulk, suspension, solution or emulsion polymerization techniques; or, they may be prepared by ionic catalysis or by means of stereospecific catalysts such as those of the type developed by Ziegler.

The comonomers which may be utilized together with the above described acrylate and methacrylate monomers for the preparation of the copolymers of this invention can be any ethylenically unsaturated monomer such, for example as styrene; alpha-methyl styrene; the acrylic, methacrylic and crotonic acid esters of aliphatic alcohols such as methyl, ethyl, propyl, butyl, isobutyl, amyl, hexyl, 2-ethyl hexyl, octyl, lauryl and stearyl alcohols; acrylic acid; methacrylic acid; crotonic acid; isoprene; acrylamide; methacrylamide; N-methylol acrylamide; acrylonitrile; methacrylonitrile; butadiene; vinyl propionate; dibutyl fumarate; dibutyl maleate; diallyl phthalate; vinylidene chloride; vinyl chloride; vinyl fluoride; vinyl acetate; ethylene; and, propylene, etc. Any of these monomers may be used either alone or in combination with one another together with one or more of the acrylate and methacrylate monomers of this invention.

The homoand copolymers of this invention, whether prepared by means of bulk, suspension, solution or emulsion polymerization techniques or by any other means, may all be effectively utilized to treat a virtually unlimited variety of solid materials regardless of whether they exhibit fibrous, porous or continuous surfaces. Among such materials are included: Textiles derived from wool, cotton, polyester, nylon, polyacrylonitrile and other synthetic fibers; glass; paper; wood; leather; fur; asbestos; brick; concrete; metal; ceramics; plastics as well as painted and plastered surfaces. Thus, for purposes of convenience, when reference is hereinafter made to applying to" or to treating or to the treatment of" such substrates, these terms are meant to encompass both the coating and/ or impregnation of porous substrates as well as the coating of impervious substrates.

These solid materials may be treated by means of any effective technique whose use is desired by the practitioner. Thus, textiles are typically treated by a padding technique wherein the textile is passed through an organic solvent solution of a novel fiuorochemical product of this invention, squeezed through a nip and then briefly heated to evaporate the solvent. Typical organic solvents include isopropanol, acetone, methyl ethyl ketone, etc. The treated textile is subsequently cured by being heated at a temperature of from about 60 C. to C. for a period of about 5 to 10 minutes, thereby developing total water and oil repellency. A Lewis acid catalyst, such as aluminum chloride, may be optionally present in order to enhance the latter curing operation. In addition, such surface coating techniques as spraying and brushing may also be effectively utilized in order to deposit a film of the repellent on the surface of the substrate. The amount of additive which is required to provide adequate water, oil and soil repellency will vary according to the particular fluorochemical product being used, the selected substrate and the specific end-use application of the resulting treated product, although the presence of as little as about 0.1% of the additive, based on the weight of the substrate, will ordinarily provide adequately improved water and oil repellency. On the other hand, it may be noted that there is no particular advantage to be derived from utilizing more than about 6% of replellent, based on the weight of the substrate, since the increased expense thus incurred far outweighs the increase in repellency which may be obtained thereby.

In addition, it is to be noted that the novel polymers of this invention may be applied to the desired substrates while they are in the form of an aqueous emulsion, it being merely necessary to polymerize them in aqueous form, or otherwise, to select an appropriate emulsifier for the polymeric system.

It should be noted that the presence of ether linkages in these monomers and polymers does not hinder oil repellency. Furthermore, these ether linkages render hydrophilic the typically hydrophobic fluorocarbon coating so that it may be wet by water. This wetability of the coating facilitates soil release of ground-in stains during wet laundering.

The actual application to substrates of the novel compositions of this invention may be accomplished by any part dimethyl stearylamine, 0.06 part glacial acetic acid, 31.8 parts water, 12.3 parts acetone, 0.02 part N-methylolacrylamide, 0.3 part N-butyl acrylate, 10 parts ethylene glycol, mono-(a,m-dihydroperfluorooctyl) ether acrylate,

means capable of effectively depositing a small concenprepared in Example I hereinabove, and 0.05 part aunt'- tration of the repellent, such as by a coating or spray azobisisobutyramidine dihydrochloride. The mixture was technique, purged for 15 minutes at room temperature with nitrogen, The following examples will further illustrate the emand then the temperature was raised to reflux (60 C.). bodiment of this invention. In these examples, all parts This temperature was maintained over a 5 hour period given are b w ight nles otherwise noted, during which time, polymerization was evidenced by an EXAMPLE I increase in turbidity. After the polymerization Was complete, the latex was filtered through cheese cloth. A 94% This example illustrates the preparation of a fiuoromonomer conversion factor was indicated. alkylalkoxyalkyl acrylate monomer typical of the novel products of this invention. i EXAMPLE III A monel reactor Was charged Wlih 205 Parts m y- This example illustrates the preparation of the novel dfoperfiuoreoetehel and 6 Parts Powdered The C011- polymers of this invention by means of a solution polymtents of the reactor were cooled to 40 C. whereupon erization technique Parts ethylene Oxide liquid was added thel'ete- I A reaction vessel fitted with a nitrogen inlet, thermomrea Was sealed to the atmosphere and heated at 90 eter, reflux condenser and stirrer was charged with 10 for 18 hours. parts ethylene glycol, mono-(a,a-dihydroperfluorooctyl) After eompletloh e the e e P the contents ether acrylate (described in Example I, hereinabove), 10.3 of the reactor were dissolved in diethyl ether and washed pal-ts acetone and 0 3 part obi i ob t o jt fl with diluted acid and then Water 11I1t11 the Wate1 WaShes The solution was purged for 15 minutes at room temperawere neutral to litmus. The ether solution was dried over 5 m and then brought to r fl x 0 c Upon initiation sodium sulfate and the ether removed by distlllation. f the polymerization reaction, as evidenced by a i Fractionation of the resulting alkylate indicated an 82.5% cosity i a 0,5 8 art of a 40%, by weight, N- yield consisting of olacrylarnide solution in isopropanol was added over a 57% C F CH OCH CH 0 mlnute period. After three hours at reflux, the reacand 7 15 2 2 2 30 tron was diluted to 30% by the addition of acetone and 0.015 part of additional catalyst was added with continued 43% '1 15 2 a 2 )2 heating for an additional three hours. An 87.5% monoth 16 e mer conversion factor was indicated. Thereafter Parts of the above prepared y This solution polymerization technique is suitable for glycol, mono-(u,u-d1hydroperfluorooctyl) ether, par s b H De preparing any of the reaction products in accordance with of glacial acrylic acid, 75 parts toluene, 0.8 part e ze h the invention. Thus, following the procedure of the Exsulfomc acid and 0.4 part monomethyl ether of y am 1e III the 0110 th 1 n t d quinone were charged into a 3-neck round bottom flask P b l s e Y l e il Y 111128 ate monofitted with thermometer, stirrer, azeotropic distillation remers,may e e tyrene, P e'met Y the acryhc, methacryhc and crotomc esters of aliphatic alcoceiver and condenser. The mixture was agitated and heat- 40 hols, acrylic acid, methacryhc acid, crotomc acid, 180- ed at its reflux temperature, 1.e. approximately 120 C.,

prene, acrylamide, methacrylamide, acrylomtrile, meth- 8 hours when 2.8 parts of water had been collected. The

acrylomtrile, butadrene, vmyl propionate, dibutyl fumartoluene solution was washed with water and dilute aqueate dibut 1 y maleate, diallyl phthalate, vmyhdene chloride, 0118 SOdlum hydroxlde Solutlon the W hquor was vinyl chloride vinyl fluoride vinyl acetate ethylene and neutral to litmus. After drying over sodium sulf the Prowlena toluene solution was fractionated thereby providing a EXAMPLE IV 78% yield of the ethylene glycol, mono-(a,a-d1hydroperfiuorooctyl) ether acrylate. (B.P. 94400" c./0.4 mm. Thls x p l es the Wlde varwty of reagents and reactlon conditions which can be efliciently utilized to The above procedure was then repeated, under identical P p the novel Prodllets 0f S ve tlonconditions, with the exception that methacrylic acid was A number of flhfiel'eht flllefo aefylate p y e s w r substituted for the acrylic acid utilized therein in order to Prepared, aeeofdlng e generalprocedure Set forth In prepare a comparable methacrylate ester. Examples I and III, utilizing a variety of reagents at different concentration levels and under varying reaction EXAMPLE II conditions. These variables are presented in the following This example illustrates the preparation of the novel tables wherein Table 1 refers to the preparation of the polymers of this invention by means of an emulsion poperfluoroalkoxyalkyl alkanol intermediates, Table II relymerization technique. fers to the preparation of the corresponding acrylate and A reaction vessel fitted with a thermometer, stirrer, methacrylate esters and Table III refers to the homoor reflux condenser and nitrogen inlet, was charged with 0.36 copolymerization of the resulting ester monomers.

TABLE I Parts Intermediate number 2 a 4 5 s 7 s a: rfl n t 1. so ili-igiiii hro p inu i i ci n if 40 40 40 5o a,a-Dihydroperfluorobutanol 35 ll-perfluoro heptyl-undecane-l-ol- 14. 8 Ethylene oxide 9.7 6 17 1. 45 Propylene oxide 8. 7 gfiZ-butyleue oxide- 7. 2 5 yrene 0X1 P a 1.2 1.3 0.6 0.6 0.3 1.5 hg e t IEii ie giQiE iEe'K" 0.)- 90 85 85 -70 110 Reaction time (hours) 20. 5 18 18 22 8 20 19 Boiling range of product C.lmm. Hg) 72-120 o.3 72-84/0 4 66-112/11 72-7710. 15 108-112/0. 13 wee/0.35

TABLE 11 Parts Monomer No 11 12 13 14 15 16 17 18 Ethylene glycol, mono (or,0:-(1ll1ydI'ODGIIlHOIOOClLYl) ether (prepared in Ex. 1) 05. 3 30 Diethylene glycol, mono (a,a-dil1ydroperfiuorooctyl) ether (prepared in Ex. 1) 71. 7

Ethylene glycol, mono (1,l,7-trihydropcrfiuoro hcptyl) ether (Intermediate #2) Ethylene glycol, mono (:,a-dil1Ydl0PBXflll0l0 butyl) ether (Intermediate #4) Diethylene glycol, mono (a,a-dil1ydroperfluoro butyl) ether (Intermediate #4) Triethylene glycol, mono (a,a-dil1ydroperfluoro butyl) other (Intermediate #4) l-methyl-ethylene glycol, mono-( ,a-dihydroperfluorooctyDcther (Intermediate #8) Ethylene lycol, mono ([ll-perfiuoro helptyl] undecyl ether (Intermediate #7) I-phenyl-ethylene glycol, mono-(a,a-dihydro pcrfiuorooctyl) ether (Intermediate #6) finorooctyl) ether (Intermediate 0 Methacrylyl chloride 5 5. 4 6. 3 Glacial acrylic acid 14 7- 2 21 8- 6 3.1 50 75 35 30 h 50 25 45 0 5 0.6 0.3 0.1a Methyl ether hydroquinone.. 1 5 0 03 0.5 0 007 0.13 Hydroquinono 0 5 0-3 0 6 Triethyl amine. Dicthyl ether... Percent yicld 98 93 86 88 93.4 67 93. 2 Boiling point C./mm. Hg) 80-110/0. 02 8090/0.3 85-90/0.2 68-104/12 105-112/0. 28 65-77/0.07 133-135/0 45 TABLE III 30 drops of testing oils, which comprised varying mixtures of Parts mineral 011 and n-heptane were gently placed upon the fabric and after a three minute period, the fabric was Polymer No 21 2 23 24 25 visually studied in order to observe the extent of wetting Ethylene glycol,mohohyumhydmpeh and penetration. A11 011 repellency rating, as defined in the glrhgroheptyl) ether acrylate (Monomer If following table, was then assigned to each fabric; the lato Ethylene glycol mhnmhafldihydmpeh ter rating corresponding to the composition of the particfluorooctyl) ether acry ate (Monomer 18 10 ular oil mixture WhlCh contained the highest percentage of #13 Ethylene glycol, mono-(a,a-dihydroperheptane and which did not penetrate or wet the fabric. fiuorooctyl) ether methacrylate Monomar #11) l-ethyl-cthylene glycol, mono'(a,a-dihy- 40 Volume percent dmperfiuomoctyl) ether methacrylate Oil repellency rating Mineral oil Heptane (Monomer #15) Methyl methacrylate. 30 70 2-ethyl hexyl acrylate..- 4o 60 N-methylol aerylamide. 5 Acetone 40 Benzene 30 Methyl alcohol. 2O lsopropyl alcohol l 100 0 02,0: -azobisisobutyronitnle Reaction temperature C.).

1 No resistance to mineral oil.

Reaction time (hours) -I: 8 7 8 7 Conversion to polymer (percent) 75 87.7 89

It is to be noted that ratings of 70 and above are indica- EXAMPLE V 50 tive of effective oil repellency. Water repellency: The water repellency of the treated ThlS example illustrates the excellent water and 011 cotton fabrics was measured by use of the Standard repellent proplartifis exhibited by substrates which have Spray Test of the American Association of Textile Chem been treated with the novel fluoro acrylate copolymers of ists and Co1oriSts AATCc No In this this invention 55 'cedure, the cotton samples which were used were prepared In order to dewmflstrate the excellent water and according to the method described, hereinabove, in the repellent characteristics of the novel copolymers of this Repehehcy Test The swatch was then Securely mvention' the followmg testmg Procedures were fastened to a 6" hoop so that it presented a smooth wrinployed- In each instance the cotton Print cloth that was kle-free surface. The test sample was positioned at a 45 U'Sed as textlle sample was treated by means of a 60 angle with its mid-point directly opposite a spray nozzle ding technique whereln the sample was passed through a so that the center of the spray pattern from the nozzle 1:1 isopropanolzmethyl ethyl ketone solution of the was, accordingly, aligned with the mjdiwint f the Selected copolymer, Squeezed through a heated at a swatch. Thereupon, 250 ml. of distilled water were sprayed low temperature in order to evaporate the solvent and onto the sample over a period of 25 to 30 seconds. The thereafter heated ata temperature of C. for a period 65 e Pattern Which formed on the surface of the test saw of 5 minutes in order to cure the thus treated fabric. pie was compared with a series of rated Standard wet Oil repellency: The oil repellency of the treated cotton patterns. Each test sample was then assigned the rating fabncs was measured by use of the 3M on Repellency of the standard pattern which most closely approximated Tcst; the latter procedure being fully described on page m a th t t 1 t 323 of the April 1962 issue of the Textile Research Jour- 70 i a fg gfi i s g hgg i l ggf patterns were nal. In this procedure, an 8" x 10" swatch of the treated cotton, which had been conditioned at a temperature of 100no sticking or wetting of upper surface 70 F. (21 C.) and a relative humidity of 65% for a 90-slight random sticking and wetting of upper surface period of 4 hours, was securely fastened to a 5" hoop in 80wetting of upper surface at spray points order to provide a smooth wrinkle-free surface. Single 75 70partial wetting of whole of upper surface 50--complete wetting of whole of upper surface (l-complete wetting of whole of upper and lower surfaces.

The results of these determinations are presented in the following table:

Percent of repellent based on weight of cotton Oil Spray Repellent (Polymer No.) fabric rating rating Control (untreated cotton swatch) 0 22 1. 110 70 1. 5 90 70 1. 5 110 70 1. 5 70 The results summarized above thus clearly show the excellent water and oil repellency exhibited by the novel fiuoro acrylate polymers of this invention.

Summarizing, it is thus seen that this invention provides a novel class of fiuoro acrylate and methacrylate esters which-may be incorporated into a Wide variety of copolymers; theJesuIting copolymers displaying excellent water, oil and soil repellency properties.

What is claimed is:

1. A composition selected from the group consisting of fluoroalkyl-alkoxyalkyl acrylate and methacrylate esters corresponding to the formula wherein Z is a radical containing from 3 to carbon atoms inclusiveand is selected from the group consisting of straight and branched chain perfluoro alkyl radicals;

perfluoro cyclo aliphatic radicals; and, straight and branched chain perfluoro alkyl and perfluoro cyclo aliphatic radicals wherein the perfluoro group is sub stituted with at least one atom selected from the group consisting of hydrogen, chlorine, bromine and iodine atoms;

X isa radical selected from the group consisting of straight 'andbranched chain alkenylene and alkylene radicals containing from 1 to 20 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl radicals containing from. 1 to 20 carbon atoms, aromatic radicals, and cycloaliphatic radicals;

R is selected from the group consisting of hydrogen and methyl 'iradicals; and,

n is an integer having a value of from 1 to 10 inclusive.

2. Acomposition exhibiting water and oil repellency properties comprising a polymer of at least one ethylenically unsaturated monomer together with at least one monomeric composition selected from the group consisting of fluoroalkyl-alkoxyalkyl acrylate and methacrylate esters corresponding to the formula 10 R is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 20 carbon atoms, aromatic radicals, and cycloaliphatic radicals; R is selected from the group consisting of hydrogen and methyl radicals; and, n is an integer having a value of from 1 to 10 inclusive.

3. The composition of claim 2, wherein said ethylenically unsaturated monomer is selected from the group consisting of styrene, alpha-methyl styrene, the acrylic, methacrylic and crotonic esters of aliphatic alcohols, acrylic acid, methacrylic acid, crotonic acid, isoprene, acrylamide, methacrylamide, N-methylol acrylamide, acrylonitrile, methacrylonitnile, butadiene, vinyl propionate, dibutyl fumarate, dibutyl maleate, diallyl phthalate, vinylidene chloride, vinyl chloride, vinyl fluoride, vinyl acetate, ethylene and propylene.

4. A process for preparing polymers which are capable of imparting water and oil repellency to solid substrates, said process comprising the step of heating at least one ethylenically unsaturated monomer, in the presence of a free radical initiator, together with at least one monomeric composition selected from the group consisting of fiuoroalkyl-alkoxyalkyl acrylate and methacrylate esters corresponding to the formula Z is a radical containing from 3 to 20 carbon atoms inclusive and is selected from the group consisting of straight and branched chain perfluoro alkyl radicals; perfluoro cyclo aliphatic radicals; and, straight and branched chain perfluoro alkyl and penlluoro cyclo aliphatic radicals wherein the perfluoro group is substituted with at least one atom selected from the group consisting of hydrogen, chlorine, bromine and iodine atoms;

X is a radical selected from the group consisting of straight and branched chain alkenylene and alkylene radicals containing from 1 to 20 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 20 carbon atoms, aromatic radicals, and cycloaliphatic radicals;

R is selected from the group consisting of hydrogen and methyl radicals; and,

n is an integer having a value of from 1 to 10 inclusive. 5. The process of claim 4, wherein said ethylenically unsaturated monomer is selected from the group consisting of styrene, alpha-methyl styrene, the acrylic, methacrylic and crotonic esters of aliphatic alcohols, acrylic acid, methacrylic acid, crotonic acid, isoprene, acrylamide, methacrylamide, N-methylol acrylamide, acrylonitrile, methacrylonitrile, butadiene, vinyl propionate, dibutyl fumarate, dibutyl maleate, diallyl phthalate, vinylidene chloride, vinyl chloride, vinyl fluoride, vinyl acetate, ethylene and propylene.

6. A solid substrate exhibiting water and oil repellency to which has been applied on at least one surface thereof a polymer of at least one ethylenically unsaturated monomer together with at least one monomeric composition selected from the group consisting of fluoroalkyl-alkoxyalkyl acrylate and methacrylate esters corresponding to the formula 6 wherein Z is a radical containing from 3 to 20 carbon atoms inclusive and is selected from the group consisting of straight and branched chain perfluoro alkyl radicals; perfluoro cyclo aliphatic radicals; and, straight and branched ,chain perfluoro alkyl and perfluoro cyclo aliphatic radicals wherein the perfluoro group is substituted with at least one atom selected from the group consisting of hydrogen, chlorine, bromine and iodine atoms;

X is a radical selected from the group consisting of straight and branched chain alkenylene and alkylene radicals containing from 1 to 20 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 20 carbon atoms, aromatic radicals, and cycloaliphatic radicals;

R is selected from the group consisting of hydrogen and methyl radicals; and,

n is an integer having a value of from 1 to inclusive.

7. The solid substrate of claim 6, wherein said ethylenically unsaturated monomer is selected from the group consisting of styrene, alpha-methyl styrene, the acrylic, methacrylic and crotonic esters of aliphatic alcohols, acrylic acid, methacrylic acid, crotonic acid, isoprene, acryl-amide, methacrylamide, N-methylol acrylamide, acrylonitrile, methacrylonitrile, butadiene, vinyl propionate, dibutyl fumarate, dibutyl maleate, diallyl phthalate, vinylidene chloride, vinyl chloride, vinyl fluoride, vinyl acetate, ethylene and propylene.

8. The solid substrate of claim 6 to which has been applied at least 0.1% of said polymer, based on the weight of said substrate.

9. A process for imparting water and oil repellency to solid substrates which comprises applying to said substrate an organic solvent solution of a polymer of at least one ethylenically unsaturated monomer together with at least one monomeric composition selected from the group consisting of fiuoroalkyl-alkoxyalkyl acrylate and methacrylate esters corresponding to the formula wherein Z is a radical containing from 3 to carbon atoms inclusive and is selected from the group consisting of straight and branched chain perfluoro alkyl radicals; perfluoro cyclo aliphatic radicals; and, straight and branched chain perfluoro alkyl and perfluoro cyclo aliphatic radicals wherein the perfluoro group is substituted with at least one atom selected from the group consisting of hydrogen, chlorine, bromine and iodine atoms;

X is a radical selected from the group consisting of straight and branched chain alkenylene and alkylene radicals containing from 1 to 20 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 20 carbon atoms, aromatic radicals, and cycloaliphatic radicals;

R is selected from the group consisting of hydrogen and methyl radicals; and,

n is an integer having a value of from 1 to 10 inclusive.

10. The process of claim '9, wherein said ethylenically unsaturated monomer is selected from the group consisting of styrene, alpha-methyl styrene, the acrylic, methacrylic and crotonic esters of aliphatic alcohols, acrylic acid, methacrylic acid, crotonic acid, isoprene, acrylamide, methacrylamide, N-methylol acrylamide, acrylonitrile, methacrylonitrile, butadiene, vinyl propionate, dibutyl fumarate, dibutyl maleate, diallyl phthalate, vinylidene chloride, vinyl chloride, vinyl fluoride, vinyl acetate, ethylene and propylene.

11. The process of claim 9 in which at least 0.1% of said polymer, based on the weight of the substrate, is applied to said substrate.

12. A composition comprising a ho'mopolymer of a monomeric composition selected from the group consisting of fiuoroalkylalkoxyalkyl acrylate and methacrylate esters correspond to the formula wherein Z is a radical containing from 3 to 20 carbon atoms inclusive and is selected from the group consisting of straight and branched chain perfluoro alkyl radicals; perfluoro cyclo aliphatic radicals; and, straight and branched chain perfluoro alkyl and perfluoro cyclo aliphatic radicals wherein the perfluoro group is substituted with at least one atom selected from the group consisting of hydrogen, chlorine, bromine and iodine atoms;

X is a radical selected from the group consisting of straight and branched chain alkylenylene and alkylene radicals containing from 1 to 20 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 20 carbon atoms, aromatic radicals, and cycloaliphatic radicals;

R is selected from the group consisting of hydrogen and methyl radicals; and,

n is an integer having a value of from 1 to 10 inclusive.

References Cited UNITED STATES PATENTS 3,527,742 9/1970 Pittmanetal 260895 3,394,115 7/1968 Sorkin 26089.5 3,547,861 12/1970 Anello et a1. 260895 3,498,958 3/ 1970 Ray-Chaudhuri et al. 260785 JOSEPH L. SCHOFER, Primary Examiner J. KIGHT III, Assistant Examiner US. Cl. X.R.

117124 E, 126 AB, 127, 132 CF, 138.8 UF, 139.5 A, 161 UC; 252-857, 8.9; 26029.6 F, 32.8 R, 33.4 R, 80.81, 83.5, 85.5 ES, 85.7, 86.1 R, 86.3, 86.7, 89.5 H, 486H Disclaimer 3,660,360.--Dilip K. Ray-Ohaizclhuri and Carmine P. Iom'nc, Somerset, NJ. WATER AND OIL REPELL NCY AGENTS. Patent dated May 1972. Disclaimer filed Sept. 28, 1976, by the assignee, National Starch and Chemical Corporation.

Hereby enters this disclaimer to claims 1, 2 and 12 of said paent.

[Official Gazette January 11, 1977.]

Notice of Adverse Decision in Interference In Interference No. 98,869 involving Patent No. 3,660,360, D. K. Ray- Ohaudhuri and C. P. Iovine, WATER- AND OIL REPELLENCY AGENTS, final judgment adverse to the patentees was rendered Apr. 6, 1976, as to claims 1, 2 and 12.

[Ofiicial Gazette June 5%, 1976.] 

